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The formation of ferrocenyl-functionalized iron and cobalt carbonyl clusters is reported, based on a reaction of FcPCl2 (3) (Fc = Fe(η5-C5H5)(η5-C5H4)) with Fe2(CO)9 and Co2(CO)8, respectively. Therein, nido-Fe3(CO)9(μ3-PFc)2 (4) and nido-Co4(CO)10(μ3-PFc)2 (5) clusters were obtained as the first diferrocenyl-substituted carbonyl clusters with a symmetrical cluster core. Cluster 4 shows two reversible one-electron processes within the anodic region, based on Fc/Fc+ redox events, as well as two processes in the cathodic region. In situ I
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